Method of water- and sunproofing paper and textiles and the composition to be used in the method



Patented Jan. 14, 1947 METHUD OF WATER- AND SUNPROOFING PAPER AND TEXTILES AND THE COMPOSI- TION TO BE USED IN THE METHOD Alvis R. Patterson, Port Saint Joe, Fla.

No Drawing. Application September 3, 1941,

Serial No. 409,381

, 16 Claims. 1 This invention relates to the treatment of teX- tiles, paper and other fibrous materials.

One object of the invention is a novel and improved composition of materials or chemicals for treating textiles, paper and other fibrous materials for the purpose of imparting to them waterproof qualities.

A further object of the invention is a composition of the character indicated above which improves the qualities of said fibrous materials when treated according to the methods herein set forth.

A further object of the invention is a novel and improved method of treatment of fibrous materials in order to improve their waterproofing qualities.

A further object of the invention is a novel and improved method of treatment of fibrous materials in order to improve their sunproof qualities.

I have found that textiles, paper and other fibrous materials may be substantially improved in quality and their waterproofing qualities enhanced by treating them with a composition or mixture of chemicals containing ferrous sulphate (FeS047I-I2O), phosphoric acid and a suitable alkali, such as pure soap or black liquor, and particularly when these constituents or ingredients are incorporated in theproportions or range of proportions indicated below. 7

The relative proportions of these ingredients may be varied within prescribed limits and I have found that a composition or mixture particularly suitable for textiles of from 3 to 30 grams of ferrous sulphate, .3 to 1 gram of phosphoric acid and .1 to 5 grams of alkali may be used to advantage.

I have found suitable a composition consisting of 30 grams of ferrous sulphate, 1 gram of phosphoric acid and 1 gram of ordinary pure soap (as for example Ivory soap), all included in solution in one quart of water. I

The range of proportions given above for textile fabrics applies generally to paper.

To obtain the desired colors of the textile fabrics and papers, dyes may be applied to the solution, which solution will then color and waterproof the textile fabric or paper fabric at the same time, In so doing, it is, not necessary to use fast dyes for the waterproofing makes a non-fast dye fast. i 7

The textilefabric-or paper fabric may be treated with the composition ormixture either by dipping the same in a bath of the composition, or the composition maybe applied to the textile or paper fabrics in any suitable manner, as, for example, by pcuringor spreading the composition on one side or both sides, as may be desired. The p r fabrics do not need to be subjected to the composition for any considerable period since they rapidly absorb the composition. Textile fabrics after being so treated may be Washed in. hot Water with the conventional washing powders and soaps Or cleaned with cleaning fluids and when dried will again be water resistant.

I have found my novel and improved composition as particularly adapted to the waterproofing of non-sized paper such as 9 point (.009) board, etc. By the treatment of 9 point board. and the like with a composition generally consisting of Dissolved in enough ordinary water to makelOOO cc. of solution;

I have very substantially increased its waterproof qualities.

While I have found phosphoric acid as the preferred acid generally to be incorporated in the composition, other acids may be employed with fairly good results, such as tannic, citric, lemon juice, tartaric, phormic, etc. I pefer ordinary pure commercial-soap such asnlvory soap, or black liquor (suchas used inthe sulphate process for makin paper), although other alkalies may be-employed, such as sodium hydroxide, etc.

, The following are other examples of suitable formulae. I

For paper, textiles, and wood, a composition of the following proportions is quite satisfactory:

Dissolved in enough water to make 1000 cc. of

solution. V

A still more specific and preferred composition for these purposes is as follows:

Ferrous-sulphate (FeSOi' IHzO) grams 5 phosphoric acid ..cc.. .0?

Soap flakes (Ivorypreferred) grams 1 Weakblaclr=-li uor,of.. about 12 IB aum If'rom the suiphate process of making pulp grams 2 Dissolve the "above in enough ordinary water to (make coo cc. of..solution. .l

This formula figures out roughly in percentages Percent Ferrous-sulphate (FeSO47I-I2O)' .5 85% phosphoric acid .007 Soap flakes (Ivory preferred) .1

or Weak black liquor of about 12 Baum from the sulphate process' o'f' making pulp .2 Ordinary water if soap flakes are used-.. 99.393

Ordinary water if black liquor is used; 99.293

Experience has shown that the following specific composition is especially good for paper, although applicable to textiles and wood also:

Ferrous-sulphate (FeSOflHiO) grams 85% phosphoric or'tartaric acid cc .0'7 Tannic acid grams 0.2 Weak black liquor; do. 2

Dissolved in enough ordinary water to make 1000 cc. of solution.

. Lemon juice and the other acids mentioned above may be used. instead of phosphoric or tartaric acid in about the same proportions as prescribed above. Tannic acid may be used in conjunction with phosphoric or tartaric to improve the gray color my process tends to give to paper, as indicated for example in the formula set forth above; If sodium hydroxide is used instead of soap or black liquorit should be used in a weaker or smaller proportion, namely about one-half 'gram or .05%-.

I may use two or more acid constituents but ordinarily I- prefer to use onlyone acid, namely phosphoric acid, particularly for textiles.

In the treatment of paper, I have found the following composition particularly suitable:

. Grams Tannic acid 1 Ferrous-sulphate 20 to 30 Black liquor. (such as used. in the sulphate process for makingpaper): of

aboutlil to SBaum 2 Citric. acid 1 Phosphoric. acid. 1

All included: in: solution in one quart of water;

For'best" results the mixture is heated to 150 F; or lukewarm temperature at time of application. The composition can be highly concentratodor" made into a powder for facilitating the handling or merchandising of the same, and whenthe composition is formed of a powder the user need only introduce it into the specified quantity of water to thoroughly dissolve and mix the same.

TeXtile fabrics or paper fabrics may be colored without affecting the water resistant qualities as pointed out above. Textiles may be dyed either along with the process of treatment or afterwards but preferably along with the composition for economy of time and cost, and this applies also to paper;

My invention is also useful in the treatment of wood" of all types, plastics and other cellulosic products for the purpose of making the same resistant to water, various other liquids, and mildew.

I have found that for best results the hyd ogen ion concentration or pH of the solution should be from 3 to 'l.'5"with' the preferred range being from 4.5 to 5.5. The exact chemical action or physical action of" my composition in imfrom the conventional paper machine.

proving the quality of articles is somewhat uncertain. However, it would appear that any free sulphuric acid hydrates 0r hydroxides that may form from ferrous sulphate are not required in water proofing, and in fact any iron hydroxide that may form in the solution is generally a hindrance rather than a help, and by having the hydrogen ion concentration not much above neutral or on the acid side the formation of iron hydroxide to. any appreciable degree is avoided. My experience. indicates that hydrates and iron hydroxides will not impart any appreciable wate proof qualities to the fibrous materials. The ferroustsulphate is believed to be the principal constituent in the waterproofing function while the phosphoric acid or other acid employed hinders or limits the precipitation (which tends to cause spotting and streaking) and acts also as a stabilizer for the solution. The alkali, as for example soap to black liquor, functions to control or limit the pH, the other ingredients having a tendency to become too acid with age, when free sulphuric acid and other equivalent acids are liberated. The black liquor or soap tends, therefore, to keep the solution at the right prescribed pH and helps to prevent the formation of these objectionable'acids.

In certain instances I have used, inaddition or solution of the ingredients mentioned above,

the phosphoric acid and the ferrous sulphate may be mixed together in solution and the fabric treated with this mixture as a first step, and then as a second step, before the fabric is dry, the same is rinsed thoroughly in a soap or black liquor solution, and as a third step rinsed in clear water before drying. This rinsing is not necessary to waterproofing but it does help to improve color and tends to improve its waterproofing qualities to a certain extent. The preferred formula for this treatment, especially for textiles, is as follows:

Ferrous-sulphate (FeSO47H2O)- grams 5 %v phosphoric acid ..c0 .07

Dissolved in enough water to make cc. of solution and heat to or lukewarm. Soak cloth in this solution from 20 minutes to. an hour.

Prepare a solution of 1 gram soap flakes in water to makelOOO cc. solution.

After cloth'has soaked in the first solution from 20 minutes to one hour rinse thoroughly in the soap solution then in clear water and dry.

The application of the composition or solution to paper may be'applied after the paper comes It may be applied, however, to the paper before it comes from the paper machine. As for example, it may beapplied at the calender stacks or between any of the drier sections, whichever is more convenient to the type of paper machine using it, or it may be: applied right after the paper. leaves the paper machine wire before it reaches the drier sections' The conventional sizing ingredients "such as rosin, alum, etc., which are incorporated in the paper during the manufacture, will be either entirely left out or reduced considerably in quantity, according to the exact type of paper desired. The use of my composition resultsin a considerable saving in the cost of materials and in the cost of the manufacture of the paper.

In the practice of my invention as applied to the treatment of ordinary unsized paper board having specifications .009-23#, .012-33#-35#, .016-42#, .016-47# and .030-90it. I have increased their waterproof qualities very substantially as indicated by the following tests. The board was immersed in water and after two and one-half hours continuous immersion in the water, it was withdrawn from the water and freed of excess water, and then weighed. Tests of around a hundred samples showed a gain in Weight by such immersion of only from around 50% to 60% on the average. These results were obtained with finished paper board treated in accordance with my invention on both sides. Waterproofing qualities may be imparted to the paper board to a substantial degree by treatment of only one side of the board, as contrasted with similar board which had not so been treated. Paper and textile fabrics may thus have their waterproofing qualities substantially increased by treatment according to my invention on only one side, and where the use of such fabric involves exposure to moisture only on one side it may be desirable to treat such fabric only on the side to be thus exposed. I have also found that paper treated in accordance with the invention j":

stands up better when subjected to the sun than papers not so treated and there is less tendency of the paper thus treated according to my in vention to disintegrate upon being wet after a sun bake than with paper not treated according to my invention.

The use of my composition or process does not preclude the use of known Waterproofing and sizing practices such, for example, as rosin sizing in the pulp and tub sizing with wax, etc., before, after, or along with treatment by my process. The added waterproofing and sunproofing qualities imparted to paper and the like by treatment under this invention probably result from the formation and deposit of ferrous oxide within the sheets, the ferrous oxide being insoluble in water and alcohol and the principal ingredients for effecting this result are the ferrous sulphate and the alkali, although it is understood that I am not bound by any theory of functioning of the composition and process. In treating paper the latter may be treated as stated above at the calender stacks or between the drier sections of the paper machine and the temperatures which in certain parts of the machine may reach 300 may also play a part in the chemical action, although quite satisfactory results have been obtained at temperatures below 300 as, for example, room temperatures.

I am aware of the fact that ferrous sulphate and other iron sulphates have been used or proposed to be used in the textile industry as mordants, etc., but I am not aware that my composition above set forth, or process of treatment, has ever been used or proposed to be used for the purpose of waterproofing and sunproofing textiles and papers.

I claim:

A composition for the treatment of textiles, paper and fibrous materials, comprising 3 to .6 grams ferrous sulphate,..3 to 3grams of an 'acid of the group consisting of phosphoric, tannic, citric, tartaric, formic, and .8 to 5 grams of weak black liquor of about 12 Baum derived from the sulphate process of making pulp'.

2. A composition for the treatment of textiles, paper and fibrous materials, comprising 3 to 30 grams ferrous sulphate; and .3 to 3 grams of'an acid constituent of the group consisting of citric, phosphoric, tannic, tartaric and formic, and an alkali in quantity from .1 to 5 grams.

3. A composition for the treatment-of textiles, paper and fibrous materials comprising around 30 grams of ferrous sulphate, around 1 gram of phosphoric acid, and around 1 gram of soap dissolved in water.

4. A method of water-proofing textiles, paper and fibrous materials which consists in subjecting it to a solution containing from 3 to 30 grams of ferrous sulphate, .3 to 3 grams of an acid and from one-half to 6 grams of an alkali, said solution having a pH of from 3 to 7.5.

5. The method of water and sun-proofing paper and textile fabrics which consists in subjecting at least one side thereof to a solution containing 3 to 10 grams of ferrous sulphate as the basic ingredient, a fraction of 1 cubic centimeter of an acid and from /2 to 6 grams of an alkali, said solution having a pH of from 3 to 7.5.

6. A composition of chemical ingredients for the treatment of textiles, paper and fibrous materials containing 3 to 30 grams of ferrous sulphate, .3 to 3 gramsof an acid and .1 to 5 grams of black liquor.

'7. The method of waterproofing textiles, paper, and fibrous materials which consists in subjecting the same to a solution containing ferrous sulphate as the basic ingredient, an acid of the group consisting of phosphoric, citric, tannic, tar taric and formic, and an alkali and in the proportions of 3 to 30 grams of ferrous sulphate, .3 to 3 grams of the acid and 1% to 6 grams of the alkali, while maintaining the solution at a pH of from 3 to 7.5.

8. In a composition of the character set forth in claim 2 wherein the alkali is black liquor.

9. In a composition of the character set forth in claim 2 wherein the alkali is soap.

10. In a composition of the character set forth in claim 2 wherein the alkali is sodium hydroxide.

11. A composition of chemical ingredients for the treatment of textiles, paper and fibrous materials containing 3 to 30 grams of ferrous sulphate, three tenths of a gram to 3 grams of an acid, and one tenth of a gram to 5 grams of an alkali.

12. In the method of claim 5 wherein the paper fabric is treated with the solution after its formation and while it is passing through the dryer sections and calender stacks of the paper machine.

13. The method of water and sun-proofing paper and textile fabrics which consists in subjecting them to a solution containing ferrous sulphate in quantity sufficient to impart water and sun-proofing qualities thereto, with the pH of the solution at from 3 to 7.5 pH.

14. The method of water and sun-proofing paper and textile fabrics which consists in subjecting them to a solution containing ferrous sulphate in quantity sufficient to impart water and sun-proofing qualities thereto, with the pH of the solution at from 3 to 7.5 and then rinsing said fabrics with a dilute soap solution.

textiles, paper and fibrous materials which consistsuin subjecting them too composition of chemical ingredients in solution containing. approximately 5 grams of ferrous su1phate,.a fraction of 1 gram of an acid, and from A of a gram to 1 gram of an alkali dissolved in water to form 1000 grams of solution.

ALVIS R. PATTERSON. 

